Radiation-sensitive polyimide precursor composition derived from a diaryl fluoro compound

ABSTRACT

A radiation-sensitive polyimide precursor composition comprises a polymer of the formula ##STR1## wherein n is a positive integer corresponding to the number of units in the polymer and is sufficiently large to provide the polymer with a number average molecular weight of about 1500-15,000 as determined by vapor pressure osmometry, and wherein for any particular unit in the polymer:→denotes isomerism; R 1  is a divalent aromatic, aliphatic or cycloaliphatic radical containing at least 2 carbon atoms; R 2  and R 3  are selected from the group consisting of a hydrogen radical and any organic radical containing a photopolymerizable olefinic double bond; and R 4  and R 5  are selected from the group consisting of perfluoro and perhalofluoro aliphatic hydrocarbons having 1 to 8 carbons.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.336,765, filed Jan. 4, 1982, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to a radiation-sensitive or photopolymerizablepolyimide precursor composition derived from a diaryl fluoro compound,especially 2,2-bis(3,4-carboxyphenyl)-hexafluoropropane dianhydride,that is useful for forming relief structures on electrical or electronicdevices such as semiconductors, capacitors, and printed circuits.

Photopolymerizable polymeric compositions used to form relief structureson electronic devices are well known as shown in, for example: U.S. Pat.No. 3,953,877, issued Apr. 27, 1976, to Sigusch et al.; U.S. Pat. No.3,957,512, issued May 18, 1976, to Kleeburg; and U.S. Pat. No.4,040,831, issued Aug. 9, 1977, to Rubner et al. (now U.S. Pat. No. Re.30,186, reissued Jan. 8, 1980).

The present invention provides for a novel radiation-sensitive polyimideprecursor composition derived from a diaryl fluoro compound, especially2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride.

SUMMARY OF THE INVENTION

A radiation-sensitive polyimide precursor composition comprises:

1. a polymer of the formula ##STR2## wherein n is a positive integercorresponding to the number of units in the polymer and is sufficientlylarge to provide the polymer with a number average molecular weight ofabout 1500-15,000 as determined by vapor pressure osmometry, and whereinfor any particular unit in the polymer: → denotes isomerism; R¹ is adivalent aromatic, aliphatic or cycloaliphatic radical containing atleast 2 carbon atoms; R² and R³ are selected from the group consistingof a hydrogen radical and any organic radical containing aphotopolymerizable olefinic double bond, at least one of R² and R³ beingsaid organic radical; and R⁴ and R⁵ are selected from the groupconsisting of perfluoro and perhalofluoro aliphatic hydrocarbons having1 to 8 carbons;

2. a radiation sensitive polymerizable polyfunctional acrylate compound;and

3. a photopolymerization initiator system comprising hydrogen donorinitiator and aromatic biimidazole.

DETAILED DESCRIPTION OF THE INVENTION

The radiation-sensitive polyimide precursor composition of the presentinvention is useful to form relief structures on electrical orelectronic devices such as capacitors and semiconductors. A solution ofthe composition is applied to a substrate such as a silicon wafer anddried to form a film on the substrate. The film is then exposed toradiation through a masking template (pattern) and photopolymerized. Theunexposed and unpolymerized part of the film is dissolved off with adeveloper solution to form a relief structure. The resulting reliefstructure is baked to eliminate the photopolymerized material and toform a polyimide structure with a sharp definition and with goodmechanical, chemical and electrical properties.

A radiation-sensitive polyimide precursor composition of the presentinvention comprises:

1. a polymer of the formula ##STR3## wherein n is a positive integercorresponding in the polymer and is sufficiently large to provide thepolymer with a number of average molecular weight of about 1500-15,000as determined by vapor pressure osmometry, and wherein for anyparticular unit in the polymer: → denotes isomerism; R¹ is a divalentaromatic, aliphatic or cycloaliphatic radical containing at least 2carbon atoms; R² and R³ are selected from the group consisting of ahydrogen radical and any organic radical containing a photopolymerizableolefinic double bond, at least one of R² and R³ being said organicradical; and R⁴ and R⁵ are selected from the group consisting ofperfluoro and perhalofluoro aliphatic hydrocarbons having 1 to 8carbons;

2. a radiation sensitive polymerizable polyfunctional acrylate compound;and

3. a photopolymerization initiator system comprising hydrogen donorinitiator and aromatic biimidazole.

In the above-described polymer wherein R⁴ and R⁵ are selected from thegroup consisting of perfluoro and perhalofluoro aliphatic hydrocarbonshaving 1 to 8 carbons, perfluoro and perhalofluoro designate materialswhich do not contain hydrogen. Instead, the hydrogen is substitutedtotally by fluorine (perfluoro) or at least 1 fluorine and anotherhalogen (perhalofluoro). In a particularly preferred composition of thepresent invention, R⁴ and R⁵ of the polymer have the formula CF₃.

The polymer of the formula ##STR4## wherein R¹, R², R³, R⁴, R⁵ and n areas defined earlier, may be prepared by one of at least two methods.

One method involves preparing the addition product of an olefinicallyunsaturated monoepoxide on a product obtained by reacting apolycarboxylic dianhydride of the formula ##STR5## where R⁴ and R⁵ areas defined earlier, with at least one organic diamine having thestructural formula

    H.sub.2 N--R.sup.1 --NH.sub.2

wherein R¹ is a divalent radical containing at least 2 carbon atoms, thetwo amino groups of said diamine each attached to separate carbon atomsof said divalent radical.

In a particularly preferred method of preparing a composition of thepresent invention, R⁴ and R⁵ of said polycarboxylic dianhydride have theformula CF₃, so that the dianhydride is2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride.

The 2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydridepreferably utilized in the reaction product described above may beprepared in the manner detailed in U.S. Pat. No. 3,310,573, issued Mar.21, 1967, to Coe; said patent being hereby incorporated by referenceinto the present disclosure.

Suitable diamines include those described in more detail in U.S. Pat.Nos. 3,179,614 and 3,179,634, both issued Apr. 20, 1965, to Edwards;said patents being hereby incorporated by reference into the presentdisclosure. Also suitable are those diamines disclosed in the Coe patent(U.S. Pat. No. 3,310,573), as well as those disclosed in U.S. Pat. No.3,959,350, issued May 25, 1976, to Rogers (also incorporated herein byreference).

Suitable diamines disclosed in the above-referenced patents to Edwardsinclude aromatic diamines of the formula

    H.sub.2 N--R.sup.1 --NH.sub.2

wherein R¹ is a divalent benzenoid radical selected from the groupconsisting of ##STR6## wherein R" is selected from the group consistingof an alkylene chain having 1-3 carbon atoms, ##STR7## where R"' and R""are radicals having 1-6 carbon atoms selected from the group consistingof alkyl and aryl. Diamines disclosed in the above-referenced patent toRogers additionally include diamines of the formula H₂ H--R¹ --NH₂wherein R¹ is ##STR8## Exemplary diamines of such structure include:4,4'-diamino-diphenyl ether;

4,4'-diamino-diphenyl sulfide;

4,4'-diamino-diphenyl sulfoxide;

4,4'-diamino-diphenyl sulfone;

4,4'-diamino-diphenyl diethylsilane;

4,4'-diamino-diphenyl diphenylsilane;

4,4'-diamino-diphenyl ethyl phosphine oxide;

4,4'-diamino-diphenyl phenyl phosphine oxide;

4,4'-diamino-diphenyl N-methyl amine;

4,4'-diamino-diphenyl N-phenyl amine;

1,3-bis(4-aminophenoxy)benzene;

1,4-bis(4-aminophenoxy)benzene; and mixtures thereof.

Suitable diamines disclosed in the above-referenced patent to Coeinclude diaryl fluoro diamines having the structure ##STR9## wherein Zand Z¹ have the formula CCl_(m) F3--m, where m is 0 to 1, A and A' areselected from the group consisting of H, Cl, Br, and NO₂.

Exemplary diamines within this structure include:

4,4'-(hexafluoroisopropylidene)-dianiline;

4,4'-(hexafluoroisopropylidene)-bis(2,6-dibromoaniline);

4,4'-(hexafluoroisopropylidene)-bis(2-nitroaniline);

4,4'-(hexafluoroisopropylidene)-bis(0-phenylene diamine);

4,4'-(hexafluoroisopropylidene)-bis(2-aminotoluene);

4,4'-(hexafluoroisopropylidene)-bis(aminobenzoic acid);

4,4'-(hexafluoroisopropylidene)-bis(2,6-dichloroaniline);

4,4'-(hexafluoroisopropylidene)-bis(N-methylaniline);

4,4'-(hexafluoroisopropylidene)-bis(N-ethylaniline);

4,4'-(hexafluoroisopropylidene)-bis(N-2-cyanoethylaniline);

4,4'-(hexafluoroisopropylidene)-bis(2-nitro-6-chloroaniline);

4,4'-(chloropentafluoroisopropylidene)dianiline;

4,4'-(chloropentafluoroisopropylidene)-bis(2,6-dibromoaniline);

4,4'-(chloropentafluoroisopropylidene)-bis(N,2-cyanoethylaniline);

4,4'-(chloropentafluoroisopropylidene)-bis(2-aminotoluene);

4,4'-(1,3-dichlorotetrafluoroisopropylidene)dianiline;

4,4'-(1,3-dichlorotetrafluoroisopropylidene)-bis(2-aminotoluene).

Any suitable solvent for reacting the polycarboxylic dianhydride withthe diamine may be used. Such suitable solvents are those organicsolvents whose functional groups do not react with either thedianhydride or diamine to a greater extent than the latter do with eachother. Besides being inert to the system and, preferably, being asolvent for the product, the organic solvent must be a solvent for atleast one of the reactants (dianhydride or diamine), preferably for bothof the reactants. A more detailed description of such suitable solventsmay be found in the two Edwards patents (U.S. Pat. No. 3,179,614 andU.S. Pat. No. 3,179,634) and the Rogers patent (U.S. Pat. No.3,959,350).

The suitable conditions for reacting the dianhydride and diamine arealso disclosed in detail in the Edwards patents and the Rogers patent.

As noted above, an olefinically unsaturated monoepoxide is added ontothe reaction product prepared from the dianhydride and diamine. Suchmonoepoxides have the formula ##STR10## wherein R⁷ is an olefinicallyunsaturated radical, preferably containing a (meth)acrylicester-containing group.

Preferred olefinically unsaturated monoepoxides are the unsaturatedepoxides glycidyl acrylate and glycidal methacrylate.

As an example, the following formula shows an addition product ofglycidyl methacrylate on the product obtained by reacting2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride with4,4'-diamine diphenyl ether: ##STR11##

Preferably, a composition of the addition product in a solvent for thedianhydride/diamine reaction, will contain about 10-50% by weight, basedon the combined weight of the addition product and solvent, of theaddition product and about 50-90% by weight of the solvent.

In preparing the addition product of the monoepoxide on adianhydride/diamine reaction product, it is advantageous to bring thedianhydride/diamine reaction product (a polyamic acid) to reaction withhydroxyethyl acrylate, hydroxyethyl methacrylate, or a combination ofthe two prior to the reaction with the olefinically unsaturatedmonoepoxide. In this manner, the end-position acid anhydride groups areintercepted or bound, and compounds with a clearly defind structure areobtained. The solubility also can be influenced by means of thisintercept reagent, and, particularly, photosensitivity of the additionproduct is enhanced due to the unsaturated nature of this interceptreagent.

A second method for preparing the polymer of the formula ##STR12##wherein R¹, R², R³, R⁴, R⁵ and n are as defined earlier, is disclosed inthe aforementioned Rubner U.S. Pat. No. Re. 30,186; said reissue patentbeing herein incorporated by reference. The Rubner method involvesesterifying an aromatic polycarboxylic acid anhydride with a hydroxyalkyl acrylate or methacrylate, then converting that esterificationproduct to a corresponding acid chloride derivative, and finallyreacting said acid chloride derivative with diamine.

The aromatic polycarboxylic acid anhydride utilized is, of course, ofthe formula ##STR13## where R⁴ and R⁵ are as described earlier. Again, aparticularly preferred dianhydride is2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride, thepreparation of which is described earlier.

Also, suitable diamines include those described above, and detailed inthe two Edwards, the Coe, and the Rogers patents.

Typical hydroxy alkyl acrylates and methacrylates are as follows:hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxy butyl acrylate,hydroxy ethyl methacrylate, hydroxypropyl methacrylate, hydroxybutylmethacryate and the like.

Thionyl chloride typically may be used to convert the esterificationproduct to a corresponding acid chloride.

Typical solvents in which the esterification of the dianhydride andsubsequent reaction of the acid chloride derivative with diamine cantake place, include butyrolactone, tetrahydrofuran, hexamethylphosphoricacid triamide, and combinations of the above. Other suitable solventsinclude those disclosed in the two Edwards and the Rogers patents andwhich do not react with the thionyl chloride or any other reagent usedto form the acid chloride derivative.

The conditions for effecting such reactions are well-known, and areexemplified in the examples of the Rubner reissue patent.

To reduce radiation exposure time and increase the rate ofphotopolymerization of a polymer product of the type described above andprepared by any method, a photopolymerizable polyimide precursorcomposition of the present invention also comprises:

1. about 5-30% by weight, based on the weight of the polymer product, ofa radiation sensitive polymerizable polyfunctional acrylate compound;and

2. about 0.5-20% by weight, based on the weight of the polymer product,of a photopolymerization initiator system comprising hydrogen donorinitiator and aromatic biimidazole.

Typically useful radiation sensitive polymerizable polyfunctionalacrylate compounds are as follows: trimethylol propane trimethacrylate,trimethylol propane triacrylate, trimethylol propane ethoxylatetrimethacrylate, trimethylol propane ethoxylate triacrylate, trimethylolpropane polyethoxylate trimethacrylate, trimethylol propanepolyethoxylate triacrylate and mixtures thereof. Preferred aretrimethylol propane polyethoxylate triacrylate having a weight averagemolecular weight of about 500-1500 and trimethylol propane ethoxylatetriacrylate, pentaerythritol triacrylate, polyethylene glycoldiacrylate, triethylene glycol diacrylate, polyethylene glycoldimethacrylate, polymethylene diacrylate, polyethylene dimethacrylate,trimethylene glycol dimethacrylate.

It is possible to photopolymerize the composition without the use of theabove polymerizable polyfunctional acrylate compounds in thecomposition. For most practical commercial processes, the presence ofthe polyfunctional acrylate compounds is highly preferred, as it reducesphotopolymerization time.

All molecular weights made reference to herein are determined by vaporpressure osmometry.

Typical aromatic biimidazole photopolymerization initiators aredisclosed by Chambers U.S. Pat. No. 3,479,185 issued Nov. 18, 1969 andCescon U.S. Pat. No. 3,784,557 issued Jan. 9, 1974 which are herebyincorporated by reference. A 2,4,5-triphenyl imidazolyl dimer having anortho substituent on the 2 phenyl ring is a particularly usefulinitiator. Typical initiators of this type are2-o-chlorophenyl-4,5-diphenyl imidazolyl dimer,2-(o-fluorophenyl)-4,5-diphenyl imidazolyl dimer,2-(o-methoxyphenyl)-4,5-diphenyl imidazolyl dimer and mixtures thereof.Particularly preferred are bis(2-o-chlorophenyl-4,5-diphenyl imidazolyl)and bis[2-o-chlorophenyl4,5-di(m-methoxy phenyl)imidazolyl] since theseinitiators are stable and are excellent photopolymerization initiators.

Also hexaaryl biimidazoles can be used as photopolymerization initiatorsas shown in Fishman U.S. Pat. No. 3,552,973 issued Jan. 5, 1971.

Typically useful hydrogen donors, photosensitizers and photoinitiatorsinclude the following: aromatic ketones such as benzophenone, Michler'sketone [4,4'-bis(dimethylamino)benzophenone],4,4'-bis(diethylamino)benzophenone,4-acryloxy-4'-diethylaminobenzophenone,4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone,phenanthraquinone, 2-t-butylanthraquinone, 1,2-benzanthraquinone,2,3-benzanthraquinone, 2,3-dichloronaphthoquinone, benzil dimethylketal, and other aromatic ketones such as disclosed in theaforementioned U.S. Pat. No. 3,552,973; benzoin, benzoin ethers such asbenzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, andbenzoin phenyl ether, methylbenzoin, ethylbenzoin and other benzoins,mercaptobenzothiazole, mercaptobenzoxazoles as disclosed in U.S. Pat.No. 4,291,115 and n-phenyl glycine.

It is possible to use combinations of both photosensitizer andphotopolymerization initiators. Generally, the photopolymerization timeis longer if the photosensitizer is not added. As thephotopolymerization is enhanced by the addition of photosensitizers,photoinitiators, or mixtures thereof, it is preferred that suchcompounds be used in the composition in amounts of about 0.1 to 15% byweight, of the composition.

It may be desirable to have a compound present that changes color whenpolymerization is complete, that is a hydrogen donor that provides arapid start for polymerization, and that is a chain transfer agent.Leuco dyes can be used such as those disclosed in the aforementionedU.S. Pat. No. 3,552,973 col. 6, line 6, to col. 11, line 9, whichdisclosure is hereby incorporated by reference. Typically useful dyesare alkyl aminoaromatic alkanes such as tris(diethylamino-o-tolyl)methane, tris(dimethylamino-o-oxylyl) methane and tris(dipropylamino-o-tolyl) methane.

Plasticizers can also be added to the composition of the presentinvention in amounts of 0.1-10% by weight, based on the weight of thepolymer product. Typical plasticizers are tricresyl phosphate, dioctylphthalate, dihexyl phthalate, dinonyl phthalate, polyethylene glycolethers, ethylene glycol dicaprolate.

In the process for applying the composition to substrates, thecomposition is applied and then dried to form a film at about 30°-100°C. for about 20 minutes to 5 hours, depending upon the coatingthickness. The film is then exposed to actinic radiation through apattern for about 1 second to 5 minutes. Preferably, for a commercialprocess exposure times of 1-60 seconds are required and usually anexposure time under 30 seconds is much preferred. Typical radiationsources used are ultraviolet lamps providing a wave length of 250 to 400nanometers and an intensity of 0.5-60 milliwatts per square centimeter(mW/cm²). After exposure, the film is then dipped or sprayed, with adeveloper solution. Typical developer solutions are4-butyrolactone/toluene in a weight ratio from 2/1 to 1/4, dimethylformamide/ethanol in a weight ratio from 2/1 to 1/4.

The film is then washed with a nonsolvent and afterwards, dried. Thefilm is cured to a polyimide relief structure by baking at about150°-450° C. for about 20 minutes to 4 hours. During curing, theacrylate components are decomposed leaving a formed polyimide structure.The resulting relief structure has a sharp definition, as well as goodchemical, electrical and mechanical properties.

Typical uses for the composition are as follows: protective coatings forsemiconductors, dielectric layers for multilayer integrated circuits,high temperature solder mask, bonding multilayer circuits, a finalpassivating coating on electrical electronic devices and the like.

The following example illustrates the invention. All parts andpercentages are on a weight basis, unless otherwise specified, andmolecular weights are determined by vapor pressure osmometry.

EXAMPLE Composition A (Polymer Product)

To a stirred solution of 33.3 grams (0.075 mol) of2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride in 115milliliters of dimethylacetamide, 11.26 grams (0.056 mol) of4,4'-diamino-diphenyl ether were added in about 2-gram lots such thatthe internal reaction temperature did not exceed 35° C. This mixture wasthen stirred at room temperature for 2 hours, after which 0.5 grams(0.004 mol) of hydroxyethyl methacrylate was added and the mixturestirred at room temperature for 2 more hours.

Then, 37.5 milliliters of glycidyl methacrylate (GMA), 0.4 grams ofbenzyldimethylamine, and 0.03 grams of hydroquinone were added in thatorder. The mixture was then warmed to between about 50° to 60° C. andstirred for 15 hours.

The reaction solution was then cooled to room temperature and washedwith 5×50 milliliters of petroleum ether to remove unreacted GMA. Thepolymer product was isolated by the dropwise addition of the reactionsolution into 1,000 milliliters of a blend of aromatic hydrocarbons(such as is sold by Union Oil Chemical Division as "Super High FlashNaphtha H-596") accompanied by vigirous stirring. The resultinggelatinous precipitate was triturated with 2×500 milliliters ofpetroleum ether and suction filtered to yield the product as a whitesolid (Composition A) with an acid number of 77.5. Infrared spectra dataindicated carbonyl frequencies of 1720 and 1630 cm⁻¹.

Composition B

A photopolymerizable polyimide precursor composition of the presentinvention was prepared by charging the following constituents into acontainer and placing the container on a roller where it was mixed for 2hours:

    ______________________________________                                        Ingredient              Amount                                                ______________________________________                                        Composition A           5.0 grams                                             Bis(2-o-chlorophenyl-4,5-                                                                             0.3 grams                                             diphenylimidazolyl)                                                           Michler's ketone (tetramethyl                                                                         0.15 grams                                            diaminobenzophenone)                                                          Tris(diethylamino-o-tolyl) methane                                                                    0.10 grams                                            Tetraethylene glycol diacrylate                                                                       0.75 grams                                            N--methylpyrrolidone    9.70 grams                                            Ethylene glycol monoethyl ether                                                                       1.70 grams                                            ______________________________________                                    

The above Composition B was filtered through a 1 micrometer filter.

A 2-inch diameter silicon wafer was coated with an aminosilane adhesionpromoter solution by a spin coating technique wherein the wafer wasrotated at 3000 rpm for 30 minutes after the adhesion promoter solutionwas applied.

Then, Composition B was applied to the wafer by the above spin techniqueusing 3000 rpm for 60 seconds. This wafer with a coating of CompositionB was then dried for 2 hours at 50° C., after which it was exposed to anultraviolet light source of 365 nanometers (nm) and an intensity ofabout 5 mW/cm², said light passing through a masking template.

The wafer was then developed by dipping it for 20 seconds in a 1/1solution of 4-butyrolactone/toluene and then rinsing it for 10 secondswith a spray of toluene to remove any unexposed composition. The waferwas then spun dry at 3000 rpm for 60 seconds. The wafer was, finally,heated and held at about 300° C. for 1 hour to provide a polyimiderelief structure of an electronic circuit, which is characterized bysharp, clean lines spaced as little as 3 microns apart, as examinedunder magnification at 150×.

What is claimed is:
 1. A radiation-sensitive polyimide precursorcomposition, comprising:a. a polymer of the formula ##STR14## wherein nis a positive integer corresponding to the number of units in thepolymer and is sufficiently large to provide the polymer with a numberaverage molecular weight of about 1500-15,000 as determined by vaporpressure osmometry, and wherein for any particular unit in the polymer:→ denotes isomerism; R¹ is a divalent aromatic, aliphatic orcycloaliphatic radical containing at least 2 carbon atoms; R² and R³ areselected from the group consisting of a hydrogen radical and any organicradical containing a photopolymerizable olefinic double bond, at leastone of R² and R³ being said organic radical; and R⁴ and R⁵ are selectedfrom the group consisting of perfluoro and perhalofluoro aliphatichydrocarbons having 1 to 8 carbons; b. a radiation sensitivepolymerizable polyfunctional acrylate compound; and c. aphotopolymerization initiator system comprising hydrogen donor initiatorand aromatic biimidazole.
 2. A radiation-sensitive polyimide precursorcomposition as recited in claim 1 wherein R⁴ and R⁵ have the formula--CF₃.
 3. A radiation-sensitive polyimide precursor composition asrecited in claims 1 or 2 wherein R² and R³ are selected from the groupconsisting of a hydrogen radical, a hydroxy alkyl acrylate radical, anda hydroxy alkyl methacrylate radical.
 4. A radiation-sensitive polyimideprecursor composition, as recited in claims 1 or 2, wherein:a. theradiation sensitive polymerizable polyfunctional acrylate compound ispresent in an amount equal to 5-30% by weight, of the polymer; and b.the photopolymerization initiator system comprising hydrogen donorinitiator and aromatic biimidazole is present in an amount equal to0.5-30%, by weight, of the polymer.
 5. A radiation-sensitive polyimideprecursor composition, as recited in claim 4 wherein R² and R³ areselected from the group consisting of a hydrogen radical, a hydroxyalkyl acrylate radical, and a hydroxy alkyl methacrylate radical.
 6. Aradiation-sensitive polyimide precursor composition, as recited in claim5, wherein said radiation sensitive polymerizable polyfunctionalacrylate compound is selected from the group consisting of trimethylolpropane trimethacrylate, trimethylol propane triacrylate, trimethylolpropane ethoxylate trimethacrylate, trimethylol propane ethoxylatetriacrylate, trimethylol propane polyethoxylate trimethacrylate,trimethylol propane polyethoxylate triacrylate, pentaerythritoltriacrylate, polyethylene glycol diacrylate, triethylene glycoldiacrylate, polyethylene glycol dimethacrylate, polymethylenediacrylate, polymethylene dimethacrylate, trimethylene glycoldimethacrylate and mixtures thereof.
 7. A radiation-sensitive polyimideprecursor composition, as recited in claim 6, in which said aromaticbiimidazole of said photopolymerization initiator is selected from thegroup consisting of bis(2-o-chlorophenyl-4,5-diphenyl and imidazolyl)and bis[2-o-chlorophenyl-4,5-di(m-methoxyphenyl)imidazolyl].
 8. Aradiation-sensitive polyimide precursor composition, as recited in claim7, wherein the composition also contains about 0.1-10% by weight, basedon the weight of the polymer, of a leuco dye.
 9. A radiation-sensitivepolyimide precursor composition, as recited in claim 8, wherein thecomposition also contains about 0.1-15% by weight, based on the weightof the polymer, of a photosensitizer.
 10. A method for the preparationof a radiation-sensitive polyimide precursor composition, as recited inclaim 1, comprising:a. reacting a polycarboxylic dianhydride of theformula ##STR15## wherein R⁴ and R⁵ are as defined in claim 1, with atleast one organic diamine having the structural formula

    H.sub.2 N-R.sup.1 -NH.sub.2

wherein R¹ is a divalent radical containing at least two carbon atoms,the two amino groups of said diamine each attached to separate carbonatoms of said divalent radical, in a suitable solvent at a temperaturebelow about 75° C. to form a carboxyl group-containing reaction product;b. reacting said reaction product with an olefinically unsaturatedmonoepoxide at a temperature from about room temperature to about 100°C. in an organic solvent to form an addition product; c. adding to asolution of said addition product, a radiation-sensitive polymerizablepolyfunctional acrylate compound; and d. also adding to said solution aphotopolymerization initiator system comprising hydrogen donor initiatorand aromatic biimidazole.
 11. A method, as recited in claim 10, whereinsaid polycarboxylic dianhydride is2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride.
 12. Amethod, as recited in claim 11, wherein said olefinically unsaturatedmonoepoxide is selected from the group consisting of glycidyl acrylateand glycidyl methacrylate.
 13. A method, as recited in claim 12 whereinsaid organic diamine is 4,4'-diamino-diphenyl ether.
 14. A method forthe preparation of a radiation-sensitive polyimide precursorcomposition, as recited in claim 1, comprising:a. reacting apolycarboxylic dianhydride of the formula ##STR16## wherein R⁴ and R⁵are as recited in claim 1, with a compound selected from the groupconsisting of hydroxy alkyl acrylates and hydroxy alkyl methacrylates toform an esterification product; b. forming an acid chloride derivativeof said esterification product; c. reacting said acid chloridederivative with a diamine of the formula

    H.sub.2 N-R.sup.1 -NH.sub.2

wherein R¹ is a divalent radical containing at least 2 carbon atoms, thetwo amino groups of said diamine each attached to separate carbon atomsof said divalent radical, to form an addition product; d. adding to asolution of said addition product, a radiation-sensitive polymerizationpolyfunctional acrylate compound; and e. also adding to said solution aphotopolymerization initiator system comprising hydrogen donor initiatorand aromatic biimidazole.
 15. A method, as recited in claim 14, whereinsaid polycarboxylic dianhydride is2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride.
 16. Amethod, as recited in claim 15 wherein said organic diamine is4,4'-diamino-diphenyl ether.
 17. A method, as recited in claim 10,wherein the reaction product of the dianhydride and diamine is broughtto reaction with a compound from the group consisting of hydroxyethylacrylate, hydroxyethyl methacrylate, and a combination of the two, priorto the reaction with said olefinically unsaturated monoepoxide.